CHAPTER-1

Introduction, Review of Voltammetry and

Theoretical Considerations
 Chapter-1

1.1. Introduction

Electrochemistry is an active field of modern research. Its plays an important role

in a practical sense for batteries, solar cells, and other energy conversion devices. The
world of biology involves in many redox reactions, as well as ion transport through
membranes and electrical conduction in the nervous system [1].

The word electrochemistry would refer to the science that studies the properties
and chemical transformations of/within ionic conductors (most commonly a solution of a
salt) and at the interface between an ionic conductor and an electronic conductor (most
commonly a metal) or semiconductor. Electrochemistry affords some of the most
sensitive and informative electroanalytical techniques such as Cyclic Voltammetry,
Stripping Voltammetry and Differential Pulse Voltammetry are not only capable of
assaying trace concentrations of an electroactive analyte, but supply useful information
concerning its physical and chemical properties. Now days it‟s applied to many other
fields such as biology and engineering, thus several researchers were explained the recent
advances in electrochemical techniques. For example; the paper by Janata on
potentiometric microsensors highlights one facet of the growing field of analytical micro
instrumentation. An elegant treatment of an emerging spectroelectrochemical method,
X-ray absorption spectroscopy, is provided by Sharpe, Heineman, and Elder. Andrieux,
Hapiot, and Saveant describe methods for the determination of rate constants of fast
reactions-sub microsecond time scales with ultra microelectrodes and nanosecond time
scales with redox catalyst techniques [2].

Sensors are the devices, which are composed of an active sensing material with a
signal “transducer”. The role of these two important components in sensors is to transmit
the signal without any amplification from a selective compound or from a change in a
reaction. These devices produce any one of the signals as electrical, thermal or optical
output signals which could be converted in to digital signals for further processing. The
sensors were classified into two types Electrochemical Sensors and Biosensors. The
Biosensors (Fig. A) is one of the devices that used specific biochemical reactions to
detect chemical compounds in biological samples such as biological proteins, nucleotides

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and even tissues [3-6].The Electrochemical sensors (Fig. B) are the device which detects
the analyte by the electrical output produced by the sensor. The combination of these two
different ways of classifications has given rise to a new type of sensors which are called
electrochemical biosensors, where the electrochemical methods are applied for the
construction and working of a biosensor [3, 7-9].

Fig. A. Biosensors Fig. B. Electrochemical sensors

In overall thesis work the Modified Carbon Paste Electrode (MCPE) was
prepared by grinding, electropolymerization, immobilization and pre-treated method for
the electrochemical investigation of paracetamol, dopamine, ascorbic acid uric acid and
lamotrigine were interfering each other during the investigation by overlapping their
voltammetric responses [10-16].

The different modified carbon paste electrode shows significant improvements of

the electrochemical sensor exhibited excellent performances for the determination some
neurotransmitters and biological drugs in physiological pH. The proposed method was
simple preparation, fast response, high sensitivity and good stability [17-20].

1.2. Voltammetry

Voltammetry is one of the groups of electroanalytical methods in which the

current is measured as a function of applied potential. The first voltammetry technique
was developed from the discovery of polarography in 1922 by the Czech chemist
Jaroslav Heyrovsky, for which he received the 1959 Nobel Prize in chemistry. From his

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invention of polarography, the voltammetry was also emerged and now it becomes one of
the branches in the field of electroanalysis. Electroanalysis can be defined as the
application of electrochemistry to solve real-life analytical problems. It has another two
branches namely, Conductometry and Potentiometry. The voltammetric technique
become most important because of the measurement of current as a function of applied
potential where in Conductometry, one can measure only current and in Potentiometry,
only potential. In voltammetry, three electrodes are used (working electrode, reference
electrode and counter/auxiliary electrode) to monitor both current and potential. Hence,
most analytical chemists‟ routinely sue voltammetric techniques for the quantitative
determination of variety of dissolved organic and inorganic substances. Inorganic,
physical and biological chemists widely use voltammetric techniques for a variety of
purpose including fundamental studies of oxidation and reduction process in various
media, kinetics of electron transfer process and thermodynamics properties of solvated
species etc.

1.2.1. Voltammetric Techniques and their Theoretical Aspects

The techniques used in the voltammetry were distinguished from the each other
by the function of potential that is applied to the working electrode to drive the
electrochemical reaction and by the material used as working electrode. Several types of
voltammetric techniques include the following:

 Linear Sweep Voltammetry (LSV)

 Staircase Voltammetry (SV)

 Square Wave Voltammetry (SWV)

 Anodic Stripping Voltammetry (ASV)

 Cathodic Stripping Voltammetry (CSV)

 Normal Pulse Voltammetry (NPV)

 Differential Pulse Voltammetry (DPV)

 Fast Scan Cyclic Voltammetry (FSCV)

 Cyclic Voltammetry (CV)

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Linear Sweep Voltammetry is a voltammetric method where the current at

a working electrode is measured while the potential between the working electrode and
a reference electrode is swept linearly in time. Oxidation or reduction of species is
registered as a peak or trough in the current signal at the potential at which the species
begins to be oxidized or reduced.

Linear sweep voltammetry involves applying a linear potential sweep to the

working electrode (the electrode under study) while monitoring simultaneously the
current flowing in the circuit. A signal generator produces a voltage sweep from Ei to Ef
and a potentiostat applies this potential wave to the electrode under study. The scan
direction can be positive or negative and in principle, the sweep rate can possess any
constant value:
Sweep rate = dE/dt

This method of analysis is commonly employed in polarography whereby under

well-defined conditions, the limiting current derived from a redox process in solution
during LSV may be used to quantitatively determine the concentration of electroactive
species in solution.

Staircase Voltammetry is a derivative of linear sweep voltammetry. In staircase

voltammetry the potential sweep is a series of stair steps. The current is measured at the
end of each potential change, right before the next, so that the contribution to the current
signal from the capacitive charging current is minimized.

Squarewave Voltammetry, a square wave is superimposed on the potential

staircase sweep [21, 22]. Oxidation or reduction of species is registered as a peak or
trough in the current signal at the potential at which the species begins to be oxidized or
reduced. In staircase voltammetry the potential sweep is a series of stair steps. The
current is measured at the end of each potential change, right before the next, so that the
contribution to the current signal from the capacitive charging current is minimized.
The differential current is then plotted as a function of potential, and the reduction or
oxidation of species is measured as a peak or trough. In this technique, the peak potential
occurs at the E1/2 of the redox couple because the current is symmetrical around the

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potential [23, 24]. Due to the lesser contribution of capacitative charging current the
detection limits for SWV are on the order of nanomolar concentrations. This technique
was invented by Ramaley and Krause and developed extensively by Osteryoungs and
their co-workers [25].

Anodic Stripping Voltammetry is a voltammetric method for quantitative

determination of specific ionic species. The analyte of interest is electroplated on
the working electrode during a deposition step, and oxidized from the electrode during
the stripping step. The current is measured during the stripping step. The oxidation of
species is registered as a peak in the current signal at the potential at which the species
begins to be oxidized. The stripping step can be either linear, staircase, square wave, or
pulse.

Cathodic Stripping Voltammetry is a voltammetric method for quantitative

determination of specific ionic species. It is similar to the trace analysis method anodic
stripping voltammetry, except that for the plating step, the potential is held at an
oxidizing potential, and the oxidized species are stripped from the electrode by sweeping
the potential positively. This technique is used for ionic species that form insoluble salts
and will deposit on or near the anodic, working electrode during deposition. The stripping
step can be either linear, staircase, square wave, or pulse.

Differential Pulse Voltammetry (Differential Pulse Polarography) is often used

to make electrochemical measurements. It can be considered as a derivative of linear
sweep voltammetry or staircase voltammetry, with a series of regular voltage pulses
superimposed on the potential linear sweep or stair steps. The current is measured
immediately before each potential change, and the current difference is plotted as a
function of potential. By sampling the current just before the potential is changed, the
effect of the charging current can be decreased.

By contrast, in Normal Pulse Voltammetry the current resulting from a series of

ever larger potential pulses is compared with the current at a constant 'baseline' voltage.
Another type of pulse voltammetry is square wave voltammetry, which can be considered

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a special type of differential pulse voltammetry in which equal time is spent at the
potential of the ramped baseline and potential of the superimposed pulse.

Fast Scan Cyclic Voltammetry is a linear sweep voltammetric technique in

which the background subtracted voltammogram gives additional information about the
electroanlyzed species. The current response over a range of potential is measured,
making it a better technique to discern additional current contributions from other
electroactive species. It is relatively fast technique with signal scans typically recorded
every 100 ms, however, the fast scan rate decrease the signal to noise ratio.

Cyclic Voltammetry is a useful technique for obtaining substantial information

about the electrochemical processes. It was first reported in 1938 and described
theoretically by Randles [26]. Cyclic voltammetry (CV) is widely used for the initial
characterization of electrochemically active systems. In addition to indicating the number
of different oxidation states, and their relative energies, CV can also be used for
mechanistic studies of systems in which the electron transfer reactions are coupled to
chemical reactions, due to the characteristic appearance of cyclic voltammograms
associated with different mechanisms [27].

1.3. Fundamentals of Cyclic Voltammetry

1.3.1. Circuit

Voltammetric analysis consists of two circuits one of which is a polarizing circuit

that applies the potential to the cell and the other is a measuring circuit that monitors the
cell current. The working electrode is potentiostatically controlled. The potential is varied
in some systematic manner and resulting current vs potential plot is known as
voltammogram.

1.3.2. Scan Rate

A simple potential waveform that is used often in electrochemical experiments is

the linear waveform i.e., the potential is continuously changed as a linear function of
time. The rate of change of potential with time is called scan rate.

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1.3.3. Switching Potentials and the Excitation Signal

Cyclic voltammetry involves the cycling of potential of an electrode between two

designated values called the Switching potentials in an unstirred solution and measuring
the resulting current. The controlling potential applied across the working electrode (WE)
and the reference electrode (RE) is called the excitation signal which is a linear potential
scan with a triangular waveform as shown in Fig. 1.1. The potential axis is also a time
that is related to scan rate [28]. The excitation signal causes the potential to scan
negatively from +0.8V to –0.2V vs SCE, at which point the scan direction is reversed
causing a positive scan back to the original potential of +0.8V. Single or multiple cycles
can be used.

1.3.4. Potential Control

The potential control of the external point is done using a potentiostat and a three
electrode system in which the potential of the WE is controlled relative to the RE,
saturated calomel electrode (SCE) or Silver-Silver chloride (Ag/AgCl) electrode. The
current passes between WE and the auxiliary electrode (AE). Because of its greater
experimental simplicity, CV has became a very popular technique for electrochemical
studies of new systems and has proved as a sensitive toll for obtaining information about
fairly complicated electrode reactions.

CV is a technique, where in a species that undergoes a reduction during a cathodic

polarization of the WE in an unstirred solution is reoxidized by applying a reverse (i.e.,
anodic) scan. The correlation of the cathodic and the anodic peak currents and differences
in cathodic and anodic potentials with the voltage scan rates has been studied
mathematically for different electrochemical reaction [29, 30]. The sweep rates in the CV
can be about the same as in single sweep voltammetry.

1.3.5. CV- An Active Electrochemical Method

CV can describe as „active‟ electrochemical method because the experiment

drives an electrochemical reaction by incorporating the chemistry in to a circuit and then
controlling the reaction by circuit parameter such as voltage.

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1.3.6. Characteristic Parameters of a Cyclic Voltammogram

The parameters of a cyclic voltammogram are peak potential and peak current.
There are two peaks associated with the redox reaction and accordingly we have the
anodic peak potential (Epa) and cathodic peak potential (Epc) and the corresponding
current associated are anodic peak current (ipa) and cathodic peak current (ipc)
respectively. Fig. 1.2 depicts a typical voltammogram for a reversible process with
current (vertical) vs potential. Since the potential varies linearly with time, the horizontal
axis can also be thought of as a time axis. More positive potentials will speed up all
oxidations and more negative potential will speed up all reductions.

1.4. Theory and Basic Principles of Cyclic Voltammetry

A linear potential sweep was obtained by cyclic voltammogram during applying

the potential to the working electrode (that is, a potential that increases or decreases
linearly with time). As the potential is sweep back and forth past the formal potential, E°,
of an analyte, a current flow through the electrode that either oxidizes or reduces the
analyte. The magnitude of this current is proportional to the concentration of the analyte
in solution, which allows cyclic voltammetry to be used in an analytical determination of
concentration.

Electron transfer plays a fundamental role in governing the pathway of chemical

reactions. Measurement of speed of electron transfer process and the number of electrons
involved are difficult in traditional experimental method like spectroscopy. Consequently
our knowledge of the driving force for many reactions remains exclusive.

Cyclic voltammetry is the most widely used technique for acquiring qualitative
information about electrochemical research. It is used in the study of electro activity of
compounds particularly biological molecules probe coupled chemical reactions
particularly to determine mechanisms, rates of oxidation/reduction reactions and also
study of electrode surfaces. It is used in all fields of chemistry as a means of studying
redox states. The electrode potential at which a drug, a metal ion or complex or some
other compounds undergoes reduction (addition of electrons) or oxidation (removal of

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electrons) can be rapidly located by cyclic voltammetry. A very important aspect of

cyclic voltammetry is its ability to generate a new redox species during the first potential
scan and then probe the species fate on the second and subsequent scans. The power of
cyclic voltammetry results from its ability considerable information on the
thermodynamics of redox process and the kinetics of heterogeneous electron transfer
reactions and on coupled chemical reactions or adsorption process. The correlation of the
cathodic and anodic peak currents and difference in cathodic and anodic peak potentials
with the voltage scan rate has been studied mathematically for different electrochemical
reaction [29, 29]. The sweep rates in cyclic voltammetry can be about the same as in
single sweep voltammetry.

Cyclic voltammetry makes possible the elucidation of the kinetics of

electrochemical reactions taking place at the electrode surface [31, 32]. In a typical
voltammogram, there can be several peaks. From the sweep-rate dependence of the
possible to investigate the role of adsorption, diffusion and coupled homogeneous
chemical reaction mechanism [33].

The important parameters of a cyclic voltammogram are the magnitudes of anodic

peak current (ipa), the cathodic peak current (ipc), the anodic peak potential (Epa) and
cathodic peak potential (Epc).The basic shape of the current verses potential response for
a cyclic voltammetry experiment as shown (Fig. 1.2). At the start of the experiment, the
bulk solution contains only the oxidized form of the redox couple so that at potenials
lower than the redox potential, i.e. the initial potential, there is no net conversion of
oxidized species (O) into reduced species (R) (point A). As redox potential is
approached, there is net cathodic current which increases exponentially with potential. As
O is converted to R, concentration gradients are set up for both O and R, and diffusion
occurs down these concentration gradients. At the cathodic peak (point B), the redox
potential is sufficiently negative that any O that reaches the electrode surface is
instantaneously reduced to R. Therefore, the current now depends upon the rate of mass
transfer to the electrode surface and so the time dependence is qt resulting in an asymetric
peak shape. Upon reversal of the scan (point C), the current continuous to decay with qt
until the potential nears the redox potential. At this point, a net oxidation of R to O occurs

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which caused a cathodic current which eventually produces a peak shaped response
(point D). If a redox system remains in equilibrium throughout the potential scan, the
electrochemical reaction is said to be reversible. In other words, equilibrium requires that
the surface concentrations of R and O are maintained at the values required by the Nernst
Equation. Under these conditions, the following parameters characterize the cyclic
voltammogram of the redox process. The peak potential separation (Epc - Epa) is equal to
57/n mV for all scan rates where n is the number of electron equivalents transferred
during the redox process. The situation is very different when the redox reaction is not
reversible, when chemical reactions are couple to the redox process or when adsorption
of either reactants or products occurs. In fact, it is these non ideal situations which are
usually of greatest chemical interest and for which the diagnostic properties of cyclic
voltammetry are particularly suited.

Since the reference electrode has a constant makeup, its potential is fixed.
Therefore any changes in the cell are ascribable to the working electrode. The control of
potential of working electrode with respect to reference electrode is equivalent of the
controlling of energy of electrons within the working electrode. As shown in Fig. 1.3,
scanning the potential in the negative direction makes the electrode a stronger reductant,
whereas scanning the potential in the positive direction makes it a better oxidant.

1.5. Applications

Cyclic voltammetry (CV) is the most effective and versatile electro analytical
technique available for the mechanistic study of redox systems [35-39]. It enables the
electrode potential to be rapidly scanned in search of redox couples once located, a
couple can then be characterized from the potential of peaks on the cyclic voltammogram
and from changes caused by variation of the scan rate. CV method have found to have
extensive application for the evaluation of thermodynamic and kinetic parameters such as
number of electron change (n), heterogeneous rate constant (k0), entropy (S), Gibb‟s free
energy (G) and diffusion coefficient (D0) etc., of a number of redox reaction associated
chemical reactions. These methods are especially useful in both oxidation and reduction
process and to study the multiple electron transfer in an electrochemical reaction [34].

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CV has become increasingly popular in all fields of chemistry as a means of

studying redox states. The method enables a wide potential range to be rapidly scanned
for reducible or oxidizable species. This capability together with its variable time scale
and good sensitivity make this the most versatile electro analytical technique. It must,
however be emphasized that its merits are largely in the realm of qualitative or
“diagnostic” experiments. CV has its ability to generate a species during one scan and
then probe its fate with subsequent scans.

1.6. Solvent

A number of physicochemical properties must be considered while choosing a

solvent for electrochemical work [35] like being in a liquid state at room temperature,
capable of dissolving electro active species of interests, having a large potential window
and having required acid-base properties. The dielectric constant is the most important
parameter for a solvent.

The cheapest solvent is water, which possesses many physico-chemical

properties. It can dissolve ionic components and form highly conducting solutions.
Water, deionized and repeatedly distilled with alkaline KMnO4, is usually considered as
pure. The purity is checked by conductivity measurements. The volatile and organic
impurities [36] are removed by passing the distilled water vapour through a column
containing Pt catalyst at about 800C over which oxygen also simultaneously passed.

Acetonitrile is perhaps a solvent with inert electrochemical properties. It has

+3.0V (versus SCE) anodic and –3.0V cathodic limits. However, this solvent has very
poor solubility for ionic species. Salts containing organic ions such as tetra-alkyl
ammonium salts must be employed.

Dimethyl formamide (DMF) is one of the aprotic solvents, which has very good
dissolving power of ionic species. It has a cathodic limit up to –3.0 V for anion radicals.
Hence, this is the solvent of choice for studies on anion radicals and dianinons. In the
positive potential regions above +1.0V, the solvent itself decomposes. Cation radicals are
less stable in this medium.

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Dimethyl sulphoxide has electrochemical properties similar to DMF in the

cathodic region. Since it is not as basic as DMF, cation radicals are somewhat stable in
this medium.

Methylene chloride is the solvent of choice for organic oxidation studies. It is

stable up to +3.0 V as acetonitrile. Cation radicals and dications are quite stable in this
medium. Electrolytes are easily soluble in methylene chloride. However, at negative
potentials of –1.0 V, the solvent decomposes. The anionic species are less stable in this
medium.

Even totally non-polar solvents such as benzene and other hydrocarbons may be
used to study the solution phase [37] as well as surface [38-42] processes. Water,
deionized and repeatedly distilled with alkaline KMnO4, is usually considered as pure.
The purity is checked by conductivity measurements. The volatile and organic impurities
[43] are removed by passing the distilled water vapour through a column containing Pt
catalyst at about 800C over which oxygen also simultaneously passed.

The main impurity present in non-aqueous solvents is water. Refluxing with

anhydrous copper sulphate, alumina, aluminum chloride, P2O5 etc., and distilling under
reduced pressure many times and collecting the proper fraction usually remove this.
Vacuum lines are employed during purification, storage and dehydrating agent such as
anhydrous alumina is added as an internal addition [44].

1.7. Supporting Electrolytes

All ionic salts or ionizable compounds in a solvent are defined as the supporting
electrolytes. It is very important to realize that they can influence the electrochemical
processes in a number of ways.

i. These electrolytes impart conductivity to the solvent and hence enable the
continuous current flow in solution.

ii. They must remain electro-inactive in the potential region of interest, if any useful
voltammetric study is to be conducted.

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iii. If the concentration of the supporting electrolyte should be very high, they can form
a space charge near the surface and the space charge potential can influence the
charge transfer kinetics.
iv. If the ions of the supporting electrolyte are adsorbed on the surface, they can
catalyze or inhibit other reactions.
v. Small cations may form ion pairs with the anion radicals formed in the electrode
Process and the properties of the ion pairs can be very different from those of the
free anion racial.
vi. Some ions may form complexes with the reactants and products.
vii. The supporting electrolyte generally controls the acidity of the ionic solution.
viii. The liquid electrolyte melts and solid electrolyte acts as the medium for the ionic
phase.

H2SO4, HClO4 and HCl are normally employed for studies in acidic aqueous
solutions and NaOH or KOH are employed for alkaline media. In neutral region, if
buffering is important, acetate, citrate and phosphate buffers are usually employed. B-R
buffer is used over a wide pH range. If the redox process does not involve acid-base
reactions, no buffers are needed and any electrolyte may be used.

Even today a number of voltammetric results at very positive potentials in KCl

media are interpreted without possible influence of Cl- adsorption. Reductions in Li+ salt
solutions are interpreted without consideration of ion pair effect. One must always
consider all possible influence of supporting electrolytes if such pitfalls are to be avoided.

Solubility is the main consideration in selecting supporting electrolyte for aprotic

solvent. A number of Tetra-Alkyl Ammonium (TAA) salts show good solubility in
aprotic media. Tetra-ethyl ammonium (TEA) salts and more recently Tetra-n-Butyl
Ammonium (TBA) salts are widely employed for this purpose.

Most of the inorganic acids, bases or salts are commercially available in the high
purity grade. TAA salts are frequently available in the form of halides. The perchlorates
or fluroborates may be easily obtained by double decomposition of these salts with the

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corresponding sodium salts. The precipitated TAAClO4 or TAABF4 may be

recrystallized twice or thrice [45].

Some electrolytes may be dehydration may be done in an oven. Dehydrated

samples should be stored in desiccators. Care must be exercised in handling explosives
salts such as NaClO4. They must neither be overheated nor ground in mortars with force
and contact with organics should scrupulously be avoided.

1.8. Electrodes

The advent of modern electrochemistry created the need for new electrodes and
electrode set-ups. The most common arrangement today is the electrochemical cell with
three different electrodes.
 Working Electrode (WE)
 Reference Electrode (RE)
 Counter/Auxiliary Electrode (AE)

1.8.1. Working Electrode

The performance of the voltammetric procedure is strongly influenced by the

material of the working electrode. The working electrode should provide high signal-to-
noise characteristics, as well as a reproducible response. Thus, its selection depends
primarily on two factors: the redox behavior of the target analyte and the background
current over the potential region required for the measurement. Other considerations
include the potential window, electrical conductivity, surface reproducibility, mechanical
properties, cost, availability, and toxicity. A range of materials have found application as
working electrodes for electroanalysis. The most popular are those involving mercury,
carbon, or noble metals.

1.8.1.1. Mercury Electrodes

Mercury is a very attractive choice of electrode material because it has a high

hydrogen overvoltage that greatly extends the cathodic potential window (compared to
solid electrode materials) and possesses a highly reproducible, readily renewable, and

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smooth surface. In electrochemical terms, its roughness factor equals unity (i.e., identical
geometrical and actual surface areas). Disadvantages of the use of mercury are its limited
anodic range (due to the oxidation of mercury) and its toxicity.

1.8.1.2. Solid Electrodes

The limited anodic potential range of mercury electrodes has precluded their
utility for monitoring oxidizable compounds. Accordingly, solid electrodes with extended
anodic potential windows have attracted considerable analytical interest. Of the many
different solid materials that can be used as working electrodes, the most often used is
carbon, platinum, and gold. Silver, nickel, and copper can also be used for specific
applications. A monograph by Adams [46] is highly recommended for a detailed
description of solid-electrode electrochemistry. An important factor in using solid
electrodes is the dependence of the response on the surface state of the electrode.
Accordingly, the use of such electrodes requires precise electrode pretreatment and
polishing to obtain reproducible results. The nature of these pretreatment steps depends
on the materials involved. Mechanical polishing (to a smooth finish) and potential
cycling are commonly used for metal electrodes, while various chemical,
electrochemical, or thermal surface procedures are added for activating carbon-based
electrodes. Unlike mercury electrodes, solid electrodes present a heterogeneous surface
with respect to the electrochemical activity [47].

1.8.1.2a. Metal Electrodes

A wide choice of noble metals is available, platinum and gold are the most widely
used metallic electrodes. Such electrodes offer very favorable electron-transfer kinetics
and a large anodic potential range. In contrast, the low hydrogen overvoltage at these
electrodes limits the cathodic potential window (to the -0.2 V to -0.5 V regions,
depending upon the pH). More problematic are the high background currents associated
with the formation of surface-oxide or adsorbed hydrogen layers. Such films can also
strongly alter the kinetics of the electrode reaction, leading to irreproducible data. These
difficulties can be addressed with a pulse potential (cleaning/reactivation) cycle, as

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common in flow amperometry [48]. The surface layers problem is less severe in
nonaqueous media where noble metals are often an ideal choice. Compared to platinum
electrodes, gold ones are more inert, and hence are less prone to the formation of stable
oxide films or surface contamination. Gold electrodes are also widely used as substrates
for self-assembled organosulfur monolayers or for stripping measurements of trace
metals. Other metals, such as copper, nickel, or silver have been used as electrode
materials in connection with specific applications, such as the detection of amino acids or
carbohydrates in alkaline medium (copper and nickel) and of cyanide or sulfur
compounds (silver). Unlike platinum or gold electrodes, the copper electrode offers a
stable response for carbohydrates at constant potential.

1.8.1.2b. Carbon Electrodes

Solid electrodes based on carbon are currently in widespread use in

electroanalysis, primarily because of their broad potential window, low background
current, rich surface chemistry, low cost, chemical inertness, and suitability for various
sensing and detection applications. In contrast, electron transfer rates observed at carbon
surfaces are often slower than those observed at metal electrodes. The electron-transfer
reactivity is strongly affected by the origin and history of the carbon surface [49, 50].
While all common carbon electrode materials share the basic structure of a six-member
aromatic ring and sp2 bonding, they differ in the relative density of the edge and basal
planes at their surfaces. The edge orientation is more reactive than the graphite basal
plane toward electron transfer and adsorption. Materials with different edge-to-basal
plane ratios thus display different electron-transfer kinetics for a given redox analyte. The
edge orientation also displays undesirably high background contributions. A variety of
electrode pretreatment procedures have been proposed to increase the electron transfer
rates. The type of carbon, as well as the pretreatment method, thus has a profound effect
upon the analytical performance. The most popular carbon electrode materials are those
involving glassy carbon, carbon paste, graphite pencil electrode, carbon fiber, screen
printed carbon strips, carbon films, or other carbon composites (e.g., graphite epoxy,
wax-impregnated graphite, Kelgraf).

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1.8.2. Reference Electrode

The potential of a working electrode in a voltammetry experiment is always

controlled with respect to some standard, and that standard is the reference electrode.
While the thermodynamic scale of half-reaction potentials found in most textbooks
measures electrode potentials against the “standard hydrogen” reference electrode (SHE),
in actual practice the SHE is much too cumbersome to use. For this reason, a number of
other reference electrodes have been developed. Experimental measurements of potential
are made against these alternate reference electrodes, and then the potentials are
“corrected” by simple addition or subtraction and reported against the SHE. One of the
most generally available reference electrodes for work in aqueous solutions is the
saturated calomel electrode (SCE). The half reaction that occurs inside of an SCE
reference is given below.

Hg2Cl2(s) + 2e– 2 Hg (l) + 2 Cl– (aq)

At 25°C, the formal potential for the SCE half reaction lies 0.2415 volts more
positive than the SHE reference electrode. A potential measured against using an SCE
can be reported versus the SHE simply by adding 0.2415 volts to it. The SCE electrode
must be constructed in an appropriate piece of glassware that can keep a small amount of
mercury in direct contact with solid calomel (Hg2Cl2) paste while at the same time
keeping the paste in contact with a saturated aqueous solution of potassium chloride.

The short hand notation for the SCE half cell is as follows:

Pt(s) / Hg(l) / Hg2Cl2(s) / KCl (aq, sat‟d) //

Electrical contact is made by immersing a platinum wire into the liquid mercury,
and the potassium chloride solution maintains ionic contact with the test solution in the
electrochemical cell via a salt bridge or porous glass frit. Such electrodes can be “home
made” or purchased from a variety of manufacturers. Other useful reference electrodes
are based on half reactions involving a silver electrode. For work in aqueous systems, the
“silver-silver chloride” or “Ag/AgCl” reference is quite popular.

17
 Chapter-1

The half reaction for this reference electrode is as follows:

AgCl(s) + e– <-----> Ag(s) + Cl– (aq)

The actual potential assumed by an Ag/AgCl reference depends only on the

activity of the chloride anion. (The other two species appearing in the half reaction are
solids which always have unit activity.). To serve as a reference, the chloride activity
needs to be held constant. To accomplish this, a silver wire (coated with a layer of silver
chloride) is immersed in an internal solution saturated with potassium chloride. The
chloride ion concentration remains fixed at the saturation limit. The short hand notation
for this reference electrode half cell is given below:

Ag(s) / AgCl(s) / KCl (aq, sat‟d), AgNO3 (aq) //

Electrical contact is made by direct connection to the silver wire, and the internal
electrode solution is placed in ionic contact with the test solution via a salt bridge or
porous glass frit.

1.8.3. Counter/Auxilary Electrode

The flow of current through the reference electrode which alters the half internal
composition was causing its potential to drift away from the expected standard value. For
this and other reason the electrochemical measurements were made without current
flowing through the reference electrode. Modern three electrode potentiostats sue a
feedback circuit to prevent this from happening, but this feedback circuit requires that an
additional auxiliary electrode by introduced into the electrochemical cell. This electrode
provides an alternative route for the current to follow, so that only a very small current
flows through the reference electrode.

The auxiliary electrode can be made from just about any material using any
desired electrode geometry. Design choices are usually based on finding a material that is
chemically inert in the particular test solution being studied and it is generally a good
idea for the auxiliary electrode to have a large surface area. In most cases, a coil of
platinum wire is used but stainless steel, copper or aluminum wire may work in non-

18
 Chapter-1

corrosive solutions where metal cation interference is not a concern. If the

electrochemical cell is made of metal, then the cell itself might be used as the auxiliary.
Because current flow at the auxiliary electrode, the electrochemical process will also
occur here. If the reduction occurs at working electrode, then at auxiliary electrode must
oxidation occurs and vice versa. The products generated at the auxiliary, if allowed to
diffuse to the working electrode, may interfere with the experimental measurement.
When this is a problem, the auxiliary electrode is placed in a separate compartment
containing an electrolyte solution that is in ionic contact with the main test solution via a
glass frit. In most cases, however, the auxiliary can be placed right in the test solution
along with the reference and working electrodes.

1.9. A Brief Literature Survey of Cyclic Voltammetric Investigation

Electron transfer plays an important role in governing the pathway of chemical

reactions. Measurement of speed of electron transfer process and the number of electrons
involved are difficult in traditional experimental method spectroscopy. Consequently our
knowledge of the driving force for many reactions remains exclusive. Electrochemical
methods offer the potential to investigate this process directly by the determination of the
number of electrons involved.

Research interests involve the study of different modified carbon paste electrodes
and the behavior of modifier on the analyte that are taken in the system, it also involve
electroploymerization, its application in simultaneous determination.

Xiao Liu et al., [51] in their study, a composite paste electrode was prepared by
mixing 10 wt% of CNTs and fine graphite powder with mineral oil and then GA was
fabricated on the surface of CNTs/MCPE. The modified carbon paste electrode showed
efficient catalytic activity in the electrochemical detection of L-Trp in the presence of
sodium dodecylbenzene sulfonate (SDBS).The PGA/CNTPE was successfully employed
to determine the concentration of L-Trp coexisting with some possible interfering
substances like uric acid (UA), ascorbic acid (AA) dopamine (DA) for simultaneous
study. In addition, modified carbon paste electrode shows high selectivity, good stability
and reproducibility, making it suitable for the routine analysis of L-Trp in clinical use.

19
 Chapter-1

Pablo R. Dalmasso et al., [52] in this work, the GCEs was modified with
MWCNT–Polyhis dispersion as a sensing layer for the highly selective quantification of
AA and/or PA in 0.050 M phosphate buffer pH 7.4. Cyclic voltammetry and differential
pulse voltammetry technique was used to investigate the electrocatalytic activity of
modified electrode and simultaneous study of AA and PA in their sample mixture. In
addition the analytical performance was also studied for GCE/MWCNT–Polyhis to
evaluated determining AA and PA in commercial pharmaceutical samples without
pretreatment

S. Chitravathi et al., [53] a polymerized film of naphthol green B was prepared on

the surface of a carbon paste electrode in Britton–Robinson (B-R) buffer solution by
electropolymerization technique. Then it was applied for the determination of DA in
presence of UA. The modified electrodes show better sensitivity and selectivity for the
determination of DA in the presence of UA when compared to unmodified electrode.
Thus the fabrication of the modified electrode has been considered in detail. This
modified electrode was used for the determination of DA and UA in pharmaceutical and
urine samples.

Li et al., [54] developed a gold nanocluster/overoxidized-polypyrrole composite

modified glassy carbon electrode by electrodeposition of gold nanoclusters on insulating
overoxidized-polypyrrole (PPyox) film modified glassy carbon electrode (GCE). They
demonstrated that the nano-Au/PPyox composite-coated exhibited stable and sensitive
current responses toward DA and 5-HT oxidation.

Maofang He et al., [55] a highly sensitive and selective method based on poly
(folic acid) modified electrode (PFA/CPE) to detect dopamine (DA) was established by
electrochemical polymerization of folic acid on a carbon paste electrode (CPE). The
PFA/CPE was characterized by scanning electron microscopy (SEM) and the
electrochemical behavior of DA at the PFA/CPE was studied. It was illustrated that the
PFA/CPE had excellent electrocatalytic ability towards the oxidation of DA.

20
 Chapter-1

Hossein Bahramipur et al., [56] the electrochemical behavior of paracetamol was

investigated at a graphene - modified carbon paste electrode by cyclic voltammetry in an
ammonium buffer solution (pH 8.5). The modified electrode showed excellent
electrocatalytic activity towards the oxidation and reduction of paracetamol resulting in a
remarkable lowering of the peak potentials and considerable improvement of the peak
currents as compared to the bare electrode.

Yang Fan et al., [57], in this paper, we prepared the Nafion/TiO2–GR composite
film modified glassy carbon electrode (GCE) for electrochemical sensing of paracetamol.
The MGCE exhibited excellent performance towards paracetamol detection, with this it
established an effective sensing and screening platform for certain pharmaceutical
preparations.

Solomon Mehretie et al., [58], in this paper, we report the poly (3,4-
ethylenedioxythiophene) GCE was prepared by cyclic voltammetric technique to know
the electrocatalytic application for the modified GC electrode. The modified electrode
was used to study the electrocatalytic activity towards the electrochemical oxidation of
paracetamol. This method developed was applied for the determination of paracetamol in
commercial tablet samples.

Edyta Wudarska et al., [59], the electrooxidation of acetylsalicylic acid (ASA) has
been investigated at a platinum electrode in aqueous solutions. The process of oxidation
and its kinetics has been investigated using cyclic and differential pulse voltammetry
thechniques. The rate constant, electron transfer coefficient and diffusion coefficients
were determined for ASA electrochemical oxidation.

Tony Thomasa et al., [60], here the electrochemical sensor was developed by
electropolymerizing Patton and Reeder‟s reagent at carbon paste electrode (CPE) for the
detection of acetaminophen (AAP). Modification improves the redox kinetics of AAP
with increased current sensitivity when compared to bare CPE and MWCNT modified
electrode, with this simultaneous determination of AAP and 4-AP was studied in their
sampal mixture. This method was successfully employed in the determination of AAP in
commercial tablets and blood serum without being subjected to pre-treatment.

21
 Chapter-1

Cheng et al., [61] studied the electropolymerization of o-Amino benzoic acid as a

modifier to fabricate a poly (o-ABA) modified GC electrode towards the oxidation of
epinephrine in the presence of ascorbic acid in 0.1 M PBS (pH.7.0). They observed that
the polymeric film modified GC electrode has excellent electrocatalytical activity on the
oxidation of epinephrine by using CV and DPV.

1.10. Faradaic and Non-Faradaic Process

Two types of process occur at electrode. One kind comprises reactions involves
the electron transfer across the metal-solution interface. Electron transfer causes
oxidation or reduction or occurs. Since the reactions are governed by Faraday‟s law (i.e.,
the amount of chemical reaction caused by the flow of current is proportional to the
amount of electricity passed), they are called Faradaic Process. Electrode at which
faradaic processes occur are sometimes called charge transfer electrodes. Under some
conditions, a given electrode-solution interface will show a range of potentials where no
charge-transfer reaction occur because such reactions are thermodynamically of
kinetically unfavourable. However, processes such as adsorption and desorption can
occur and the structure of the electrode-solution interface can change with changing
potential or solution composition. These processes are called Non-faradaic Processes.
Although charge does not across the interface, external currents can flow (at least
transiently) when the potential, electrode area or solution composition changes, both
faradaic and non-faradaic process occurs when electrode reaction takes place. Although
faradaic process are usually of primary interest in the investigation of an electrode
reaction (except in studies of the nature of the electrode-solution interface itself), the
effects of the non-faradaic processes must be taken into account in using electrochemical
data or obtain information by discussing about the charge transfer and associated
reactions.

1.11. Polarisable and Non-Polarisable Interface

All electrode-solution interfaces can be classified as polarisable or non-

polarisable. An electrode for which an electron can pass easily across the interface is

22
 Chapter-1

called non- polarisable. In this case, external application of a change of potential may
result in more electrons passing rapidly across the interface. Thus, there is a negligible
build-up of excess charge in the electrode surface, i.e., the interface does not polarize.
Platinum in contact with hydrochloric acid is a non- polarisable interface. In contrast
when the transfer of electrons is difficult, a potential change from outside will induce a
substantial build-up of excess charges at the interface, hence, the electrodes is termed
polarisable. When a potential is applied externally to the electrode the transfer of
electrons was negligible. That is, a small change in current flow causes a large change in
electrode potential. An ideally polarisable interface is one which can allow the passage of
current without causing a change in the potential difference across it. In addition, when
the current associated with charging the electrode-electrolyte interface arises purely from
capacitive effect; such an interface is termed an ideally polarisable electrode. while no
real electrode behaves ideally over the entire potential rage, some electrode-solution
system, over limited potential ranges, can show behavior which is approximately, ideal
for instance, a mercury electrode in contact with a de-aerated potassium chloride solution
which behaves as an ideal polarisable electrode at potential in excess of 1.5V.

1.12.1. Electrodes Processes

The reaction taking place between the electrode surface and species within the
solution can proceed through a series of steps that causes the conversion of the dissolved
oxidized species (O) to reduced species (R) in solution (Fig.1.4). The electrode reaction
rate is governed by the reaction rates such as
 Mass transfer
 Electron transfer of non-adsorbing species

Chemical reactions preceding or following the electron transfer which could be

homogeneous such as protonation or dimerization‟ or heterogeneous ones like catalytic
decompositions on the electrode surfaces, other surface reactions such as adsorption,
desorption, crystallisation etc.

The simplest reaction involves only mass transfer of reactant to the electrode,
heterogeneous electron transfer involving non adsorbed species and the mass transfer of

23
 Chapter-1

the product to the bulk solution. More complex reaction sequence involving a series of
electron transfer, protonations, branching mechanisms, parallel paths or modifications of
the electrode surfaces are quite common. When a steady state current is obtained, the
rates of all reactions steps are the same. The magnitude of this current is often limited by
the inherent sluggishness of one or more reactions called rate determining steps. The
more facile reactions are then held back from maximum rates by the slowness with which
such steps disposes of their products or create their participants [62, 63].

1.12. Mass Transfer Processes

Whenever an electrochemical charge transfer process takes place at the electrode

surface, the electroactive material gets depleated and a concentration gradient is set up.
Under such conditions the reactant diffuse towards the electrodesurface and the
corresponding product of the electrode reaction diffuses away from the electrode surface.
Mass transfer in electrochemistry illustrates the movement of electroactive species from
differences in electrical or chemical potential at the two locations. There are three forms
of mass transport namely, convection, migration and diffusion which influence and
electrolysis reaction (Fig. 1.5).

Convection is the process independently taking place by the discharge process, a

solution is stirred or when in the solution is present a temperature or a density gradient. In
this case the molecules of the solvent and the analyte move themselves with a more or
less troublesome motion, but that become more laminar in the vicinity of the electrode
surface. The layer of solution closer to the electrode surface is practically stationary.

Migration is the process of moving due to the attraction force of the electric field
generated by the electrode toward every ion having opposite charge and also due to the
contemporary repulsion force of every ion having the same charge of the electrode.

Diffusion is the spontaneous movement of those chemical compounds subjected

to a concentration gradient that means a situation in which a zone of the solution is poorer
than another with the process of diffusion the system tries to destabilize its homogeneity.
The diffusion speed is directly proportional to concentration gradient and then to the
concentration of the electro active compound in the solution.

24
 Chapter-1

1.13. Electron Transfer or Charge Transfer Process

The electron transfer at the interface between the electrode and electrolyte is
central to an electrode reaction. Electroactive species having moved from the bulk of the
solution by either diffusion or under forced convection enters n the electrical double
layer, which is under direct influence of the electrode. The electron transfer process can
be
 Reversible process
 Irreversible process
 Quasi-reversible process

1.13.1. Reversible Electron Transfer Process

For a reversible process, oxidation and reduction peak is observed as shown in

Fig.1.6. Reversibility can be defined as chemical or electrochemical. In an
electrochemically reversible process the electron transfer is not rate limiting. For a
chemically reversible process, both forms of redox couple (O for oxidized form and R for
reduced form) are stable in the time scale of measurement. The rate of electron transfer is
fast compared to the rate of mass transport and does not control the overall rate. In this
process the rate of reaction is fast enough to maintain equal concentration of the oxidized
and reduced species at the surface of electrode. The concentration Cox and Cred of
oxidized and reduced forms of the redox couple respectively follow the Nernst equation

E = Eo + RT/ nF ln Cox / Cred

where, n= no. of electrons transferred, F= Faraday constant, R= Gas constant and

T=temperature. If the system is diffusion controlled then the Fick‟s law of diffusion holds
for both oxidation and reduction. Under these conditions, peak current given by Randles
Sevcik equation;

ip = (2.69 x 105) n3/2 A D1/2 C0 v ½

where, n is the stoichiometric number of electrons involved in the electrode reaction, A is

the area of electrode in cm2, Do is the diffusion coefficient of the species O in cm2s-1, Co
is the concentration of the species O in mol/cm3and v is the scan rate in Vs-1.

25
 Chapter-1

Diagnostic Tests for Cyclic Voltammograms of Reversible System at 25C

i. Ep = Epa-Epc = 59/n mV, where n is number of electrons change

ii. ipc/ipc = 1
iii. ip  1/2
iv. Ep is independent of 

1.13.2. Irreversible Electron Transfer Process

For an irreversible process, only forward oxidation or reduction peak is observed

but at times with a weak reverse peak (Fig. 1.7). This process is usually due to slow
electron exchange or slow chemical reactions at the electrode surface [64]. In an
irreversible electrode process, the mass transfer step is very fast as compared to the
charge transfer step. For an Irreversible reaction, the peak current is given by [65]

ip = 2.99 x 105 n (n)1/2 A D01/2 1/2 Co

(na) = 47.7/Ep- Ep/2

The value of Ep, the difference between the cathodic and anodic peak is of the
order of 59 mV/n is given by equation. The peak separation Ep is a factor determining the
reversibility or irreversibility of an electrode reaction. The equation by Nicholson is
normally used to calculate electron transfer rate constants.

Diagnostic Tests for Cyclic Voltammograms of Irreversible System at 25C

i. No reverse peak
ii. ip  1/2
iii. Ep shifts = 30/na mV, where  is charge transfer coefficient
iv. [Ep-Ep/2] = 47.7/na mV

1.13.3. Quasi Reversible Electron Transfer Process

This is a class of electrode reactions in which the rates of charge transfer and
mass transfer are comparable or competitive. Quasi-reversible process is intermediate

26
 Chapter-1

between reversible and irreversible systems (Fig. 1.8). The current due to quasi-reversible
processes is controlled by both mass transport and charge transfer kinetics [66]. The
process occurs when the relative rate of electron transfer with respect to that of mass
transport is insufficient to maintain Nernst equilibrium at the electrode surface. In the
quasi-reversible region both forward and backward reactions make a contribution to the
observed current.

Diagnostic Tests for Cyclic Voltammograms of Quasi-Reversible System at 25C

i. ip increases with scan rate, but is not proportional to scan rate.
ii. ipc/ipa = 1, provided c=a = 0.5
iii. Ep is greater than 59/n mV and its increases with increasing scan rate
iv. Epc shifts negatively with increasing 

1.14. Objectives and Scope

The focus of the work covered in this thesis is to controllably alter the properties
of carbon surfaces by electropolymerisation method, modifiers, immobilization using
cyclic voltammetric technique, so that the surfaces are useful for desired sensor
applications

The present work is also aimed at investigating the electrochemical studies and
elucidation of the sequence of electron transfer and chemical reactions that occur at or
near the electrode surface. Research interests involve the study of reactive intermediates
that are formed when compounds are reduced or oxidised electrochemically

The aspects investigated are reversible/irreversible or coupled nature of electron

transfer, number of electrons involved, kinetic and diffusion controlled processes, effect
of concentration of electroactive species on the redox pathways, pH, nature of the
intermediates formed, nature of the products formed etc.

More emphasis has been given not only to the electrochemical behaviour of
dopamine, ascorbic acid and uric acid but also the versatility of use of carbon paste. The

27
 Chapter-1

preparation and characterization of bare and chemically modified carbon paste electrode
surface has been studied. Thorough characterization of carbon paste electrode before
modification has been studied. The electrochemical properties, carbon composition and
surface roughness of both the surface are examined.

In recent work we develop the electrochemical sensors for the detection of UA,
DA, NE, EP, 5-HT, AA, PA and FA etc these neurotransmitters are present in the
extracellular fluid of the central nervous system. Normally we believed that the direct
redox reactions of these species at bare electrodes show irreversible and high over
potential. Moreover, the direct redox reaction of these species takes place at very similar
potentials and often suffers from pronounced fouling effects, which results in rather poor
selectivity, selectivity and reproducibility. Hence Carbon was the chosen surface, as it is
highly conducting with a wide potential window, structurally stable, relatively
inexpensive and stable layers of modifiers can attach to the surface in a controllable
manner. There are many different forms of conducting carbon materials including glassy
carbon (GC), highly oriented pyrolytic graphite (HOPG), pyrolysed photoresist
film,(PPF), carbon nanotubes, carbon powder, screen printed carbon, carbon fibres,
carbon nanocapsules, Fullerene and carbon composites [67].

28
 Chapter-1

Fig. 1.1. Variation of the applied potential as a function of time in a cyclic voltammetry
experiment

29
 Chapter-1

Fig. 1.2. A typical cyclic voltammogram of current verses potential

Fig. 1.3. Potential-current axes for cyclic voltammetry

30
 Chapter-1

Fig. 1.4. General pathway of electrode-mediated processes of oxidized (O) and reduced
(R) electroactive species.

31
 Chapter-1

Fig. 1.5. Modes of mass transport

32
 Chapter-1

Fig. 1.6. Typical voltammogram for a reversible process

Fig. 1.7. Typical voltammogram for an irreversible process

33
 Chapter-1

Fig. 1.8. Typical voltammogram for a quasi-reversible process

34
 Chapter-1

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